Pentacoordinate copper systems

The electrochemical behavior of tetracoordinated Cu(i) complexes (i.e., Cu(dpp)2-based cores) is well established.193,941 The reversible redox potential for the Cu(ii)/ Cu(i) transition is around 0.6-0.7 V versus SCE. This relatively high potential underlines the stability of the 4-coordinate Cu(i) complexes relative to their Cu(n) counterparts. The redox potential of pentacoordinated copper complexes 84 86 is observed in a much more cathodic range. For example, for the 5-coordinate complex Cu(l, dap)2+/+ (dap = 2,9-di-p-anisyl-l, 10-phcnanthrolinc), in which the terpy fragment of the ring is bound to the metal, the redox potential is -0.035 V. This potential shift when going from tetracoordinated to pentacoordinated copper systems is due to the better stabilization of the Cu(ii) state, thanks to the presence in the coordination sphere of live donor atoms. 

The cyclic voltammetry behavior of the Cu(II) rotaxane, 4(5)2+ (Fig. 14.8b), is very different from that of 4, t l +. The potential sweep for the measurement was started at - 0.9 V, a potential at which no electron transfer should occur, regardless of the nature of the surrounding of the central Cu(II) center (penta- or tetracoordinate). Curve i shows two cathodic peaks a very small one, located at + 0.53 V, followed by an intense one at —0.13V. Only one anodic peak at 0.59 V appears during the reverse sweep. If a second scan ii follows immediately the first one i, the intensity of the cathodic peak at 0.53 V increases noticeably. The main cathodic peak at —0.15 V is characteristic of pentacoordinate Cu(II). Thus, in 4(5)2+ prepared from the free rotaxane by metalation with Cu(II) ions, the central metal is coordinated to the terdentate terpyridine of the wheel and to the bidentate dpp of the axle. On the other hand, the irreversibility of this peak means that the pentacoordinate Cu(I) species formed in the diffusion layer when sweeping cathodically is transformed very rapidly and in any case before the electrode potential becomes again more anodic than the potential of the pentacoordinate Cu2 + /Cu+ redox system. The irreversible character of the wave at —0.15 V and the appearance of an anodic peak at the value of + 0.53 V indicate that the transient species, formed by reduction of 4(5)2 +, has undergone a complete reorganization, which leads to a tetracoordinate copper rotaxane. The second scan ii, which follows immediately the first one i, confirms this assertion. 

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